- Nematic to smectic texture transformation in MBBA by in situ synthesis of silver nanoparticles
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The present study describes the texture changes in 'nematic' N-(4-methoxybenzylidene)-4-butylaniline (MBBA) by in situ synthesis of silver nanoparticles in the system without any external reducing or stabilizing agents. Optical polarizing microscopy (OPM), differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and scanning and transmission electron microscopy (SEM and TEM) were utilized to understand the mechanistic details of the texture transformation in MBBA. The experimental results collectively suggest that the silver nanoparticles are generated through the reduction of silver ions by MBBA upon heat treatment, followed by a clear texture transformation from 'nematic' to 'smectic'. The 'smectic' MBBA - Ag NP conjugate forms a stable luminescent glassy phase on rapid cooling, with an emission maximum of 500 nm upon photo-excitation at the silver plasmon absorption. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010.
- Sudhadevi Antharjanam,Prasad, Edamana
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Read Online
- Dibenzothiophene Sulfoximine as an NH3 Surrogate in the Synthesis of Primary Amines by Copper-Catalyzed C?X and C?H Bond Amination
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Readily accessible dibenzothiophene sulfoximine is an NH3 surrogate allowing the preparation of free anilines by copper-catalyzed cross-coupling reactions with aryl iodides or amides followed by radical S?N bond cleavage. The one-pot/two-step r
- Li, Zhen,Yu, Hao,Bolm, Carsten
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Read Online
- Electric-field modulation of component exchange in constitutional dynamic liquid crystals
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(Figure Presented) Playing the field: Application of an electric field to the thermodynamic equilibria of constitutionally dynamic sets of imines and amines that contain an imine with liquid-crystalline properties and a negative dielectric anisotropy leads to the amplification of the constituent that couples most strongly to the electric field, namely the liquid crystal (LC, see example). The field can thus induce a liquid to nematic phase transition.
- Giuseppone, Nicolas,Lehn, Jean-Marie
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Read Online
- Scalable Negishi Coupling between Organozinc Compounds and (Hetero)Aryl Bromides under Aerobic Conditions when using Bulk Water or Deep Eutectic Solvents with no Additional Ligands
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Pd-catalyzed Negishi cross-coupling reactions between organozinc compounds and (hetero)aryl bromides have been reported when using bulk water as the reaction medium in the presence of NaCl or the biodegradable choline chloride/urea eutectic mixture. Both C(sp3)-C(sp2) and C(sp2)-C(sp2) couplings have been found to proceed smoothly, with high chemoselectivity, under mild conditions (room temperature or 60 °C) in air, and in competition with protonolysis. Additional benefits include very short reaction times (20 s), good to excellent yields (up to 98 %), wide substrate scope, and the tolerance of a variety of functional groups. The proposed novel protocol is scalable, and the practicability of the method is further highlighted by an easy recycling of both the catalyst and the eutectic mixture or water.
- Dilauro, Giuseppe,Azzollini, Claudia S.,Vitale, Paola,Salomone, Antonio,Perna, Filippo M.,Capriati, Vito
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supporting information
p. 10632 - 10636
(2021/04/09)
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- Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
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A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]
- Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
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- Superhydrophobic nickel/carbon core-shell nanocomposites for the hydrogen transfer reactions of nitrobenzene and N-heterocycles
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In this work, catalytic hydrogen transfer as an effective, green, convenient and economical strategy is for the first time used to synthesize anilines and N-heterocyclic aromatic compounds from nitrobenzene and N-heterocycles in one step. Nevertheless, how to effectively reduce the possible effects of water on the catalyst by removal of the by-product water, and to further introduce water as the solvent based on green chemistry are still challenges. Since the structures and properties of carbon nanocomposites are easily modified by controllable construction, a one step pyrolysis process is used for controllable construction of micro/nano hierarchical carbon nanocomposites with core-shell structures and magnetic separation performance. Using various characterization methods and model reactions the relationship between the structure of Ni?NCFs (nickel-nitrogen-doped carbon frameworks) and catalytic performance was investigated, and the results show that there is a positive correlation between the catalytic performance and hydrophobicity of catalysts. Besides, the possible catalytically active sites, which are formed by the interaction of pyridinic N and graphitic N in the structure of nitrogen-doped graphene with the surfaces of Ni nanoparticles, should be pivotal to achieving the relatively high catalytic performance of materials. Due to its unique structure, the obtained Ni?NCF-700 catalyst with superhydrophobicity shows extraordinary performances toward the hydrogen transfer reaction of nitrobenzene and N-heterocycles in the aqueous state; meanwhile, it was also found that Ni?NCF-700 still retained its excellent catalytic activity and structural integrity after three cycles. Compared with traditional catalytic systems, our catalytic systems offer a highly effective, green and economical alternative for nitrobenzene and N-heterocycle transformation, and may open up a new avenue for simple construction of structure and activity defined carbon nanocomposite heterogeneous catalysts with superhydrophobicity.
- Duan, Zhiying,Liu, Fangfang,Pang, Shaofeng,Su, Qiong,Wang, Yanbin,Xie, Xin,Zhang, Ping,Zhang, Yujing,Zhou, Feng
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p. 1996 - 2010
(2020/04/07)
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- From alkylarenes to anilines via site-directed carbon–carbon amination
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Anilines are fundamental motifs in various chemical contexts, and are widely used in the industrial production of fine chemicals, polymers, agrochemicals and pharmaceuticals. A recent development for the synthesis of anilines uses the primary amination of C–H bonds in electron-rich arenes. However, there are limitations to this strategy: the amination of electron-deficient arenes remains a challenging task and the amination of electron-rich arenes has a limited control over regioselectivity—the formation of meta-aminated products is especially difficult. Here we report a site-directed C–C bond primary amination of simple and readily available alkylarenes or benzyl alcohols for the direct and efficient preparation of anilines. This chemistry involves a novel C–C bond transformation and offers a versatile protocol for the synthesis of substituted anilines. The use of O2 as an environmentally benign oxidant is demonstrated, and studies on model compounds suggest that this method may also be used for the depolymerization of lignin.
- Liu, Jianzhong,Qiu, Xu,Huang, Xiaoqiang,Luo, Xiao,Zhang, Cheng,Wei, Jialiang,Pan, Jun,Liang, Yujie,Zhu, Yuchao,Qin, Qixue,Song, Song,Jiao, Ning
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- Aromatic amine compound synthesis method
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The invention discloses an aromatic amine compound synthesis method which is characterized in that the method is implemented according to any of two methods. The first method includes the steps: mixing an alkyl aromatic compound with a general formula (I) and a nitrogen-containing compound with a general formula (II); performing reaction on mixture under an oxidizing agent and an organic solvent to obtain an aromatic amine compound with a general formula (III). The second method includes the steps: mixing an aromatic alcohol derivative with a general formula (I') and the nitrogen-containing compound with the general formula (II); performing reaction on mixture under an acid additive and an organic solvent to prepare the aromatic amine compound with the general formula (III). According to the method, a lot of alkyl aromatic compounds or aromatic alcohol derivatives firstly serve as raw materials, and the raw materials are reacted to generate the aromatic amine compound without the action of metal catalysis. Compared with a traditional synthesis method, the synthesis method has the advantages that the method is high in yield and simple in condition, waste discharging amount is less,metal participation is omitted, a reaction device is simple, industrial production is easily achieved and the like. The method has a wide application prospect.
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Paragraph 0121-0123
(2019/01/23)
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- Catalytic synthesis method of p-n-butylaniline
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The invention relates to the field of organic synthesis, and discloses a catalytic synthesis method of p-n-butylaniline. The catalytic synthesis method comprises the following steps that (1) aniline,butanol and acid modified graphite phase carbon nitride are placed in a reactor, the temperature is raised to 150-170 DEG C, and is kept for areaction for 5-7 h; (2) then the temperature is raised to230-250 DEG C, and is kept for a reaction for 9-11 h; and (3) a reactant is taken for reflux in alkali liquor, and is separated and dried to obtain a crude product of the p-n-butylaniline. According to the catalytic synthesis method, the acid-modified graphite phase carbon nitride is used as a catalyst for the synthesis reaction of the p-n-butylaniline, the good catalytic activity is achieved, theyield of the p-n-butylaniline is high, meanwhile the acid-modified graphite phase carbon nitride is very environment-friendly, non-toxic and pollution-free, corrosion and damage to equipment are avoided, and an environment-friendly catalyst is achieved.
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Paragraph 0024-0054
(2019/11/12)
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- Synthesis of 4 - n-alkyl substituted phenol method
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The invention discloses a synthesis method of 4-n-alkyl substituted phenol. Under the catalysis of zinc chloride, aniline and n-alkyl alcohol with the carbon number being 4-30 react in methylbenzene or xylene to obtain the 4-n-alkyl substituted aniline, and then the 4-n-alkyl substituted aniline reacts with sodium nitrite and acid to obtain the 4-n-alkyl substituted phenol. The synthesis method is easy to implement, an intermediate directly enters the next reaction without being separated or purified, and therefore the reaction efficiency is improved. The final product is high in purity and is good in depth of parallelism when reappearing, and technological conditions are suitable for mass production.
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Paragraph 0017-0020
(2018/04/01)
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- ICI 56,780 optimization: Structure-activity relationship studies of 7-(2-phenoxyethoxy)-4(1H)-quinolones with antimalarial activity
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Though malaria mortality rates are down 48% globally since 2000, reported occurrences of resistance against current therapeutics threaten to reverse that progress. Recently, antimalarials that were once considered unsuitable therapeutic agents have been revisited to improve physicochemical properties and efficacy required for selection as a drug candidate. One such compound is 4(1H)-quinolone ICI 56,780, which is known to be a causal prophylactic that also displays blood schizonticidal activity against P. berghei. Rapid induction of parasite resistance, however, stalled its further development. We have completed a full structure-activity relationship study on 4(1H)-quinolones, focusing on the reduction of cross-resistance with atovaquone for activity against the clinical isolates W2 and TM90-C2B, as well as the improvement of microsomal stability. These studies revealed several frontrunner compounds with superb in vivo antimalarial activity. The best compounds were found to be curative with all mice surviving a Plasmodium berghei infection after 30 days.
- Maignan, Jordany R.,Lichorowic, Cynthia L.,Giarrusso, James,Blake, Lynn D.,Casandra, Debora,Mutka, Tina S.,LaCrue, Alexis N.,Burrows, Jeremy N.,Willis, Paul A.,Kyle, Dennis E.,Manetsch, Roman
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p. 6943 - 6960
(2016/08/05)
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- Ti(O-i-Pr)4/Me3SiCl/Mg-mediated reductive cleavage of sulfonamides and sulfonates to amines and alcohols
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A low-valent titanium generated in situ from Ti(O-i-Pr)4, Me3SiCl, and Mg powder in THF reacted with aryl- and alkyl-sulfonamides of aryl and alkyl amines in a reductive N-S/S-O/S-C bond cleaving pathway to provide the corresponding amines and hydrocarbons (and thiols) derived from the sulfonyl moiety. The reagent could also cleave sulfonates to the corresponding alcohols.
- Shohji, Noriaki,Kawaji, Tsuyoshi,Okamoto, Sentaro
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supporting information; experimental part
p. 2626 - 2629
(2011/07/08)
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- Liquid-crystalline polymorphism of symmetrical azobananas: Bis(4-(4-alkylphenyl)azophenyl) 2-nitroisophtalates
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In this paper we present a series of novel compounds, bis(4-(4-alkylphenyl) azophenyl) 2-nitroisophtalates, which exhibit nematic and banana-type liquidcrystalline phases. The alkyl chain length varies from 1 to 18 carbons. The first ten members of this series exhibit nematic phase. The last eleven compounds exhibit banana-type liquid crystalline phases. The propyl and pentyl derivatives have extra second type of banana mesophase. Copyright Taylor & Francis Group, LLC.
- Zygadlo,Dardas,Nowicka,Hofmann,Galewski
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scheme or table
p. 283 - 291
(2011/08/02)
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- Synthesis of enantiopure 1-aryl-1-butylamines and 1-aryl-3-butenylamines by diastereoselective addition of allylzinc bromide to imines derived from (R)-phenylglycine amide
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The synthesis of enantiopure 1-aryl-1-butylamines via a highly diastereoselective addition of allylzinc bromide to imines derived from (R)-phenylglycine amide is reported. These are synthesised by a three-step procedure, which involves: (a) formation of the chiral imines; (b) asymmetric addition of the allylzinc reagent; (c) removal of the chiral auxiliary by means of a reductive or non-reductive method. The reductive method provides 1-aryl-1-butylamines whereas the non-reductive method preserves the double bond to afford 1-aryl-3-butenylamines. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Dalmolen, Jan,Van Der Sluis, Marcel,Nieuwenhuijzen, Jose W.,Meetsma, Auke,De Lange, Ben,Kaptein, Bernard,Kellogg, Richard M.,Broxterman, Quirinus B.
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p. 1544 - 1557
(2007/10/03)
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- Palladium-catalyzed synthesis of arylamines from aryl halides and lithium bis(trimethylsilyl)amide as an ammonia equivalent
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(Equation presented) A simple, palladium-catalyzed method to convert aryl halides to the parent anilines using lithium bis(trimethylsilyl)amide (LiN(SiMe3)2) is reported. The reaction is catalyzed by Pd(dba)2 and P(t-Bu)3 and can be run with as little as 0.2 mol % of catalyst. The reaction is faster than competing generation of benzyne intermediates and, therefore, provides the aniline products regiospecifically.
- Lee, Sunwoo,Jorgensen, Morten,Hartwig, John F.
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p. 2729 - 2732
(2007/10/03)
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- Indium Mediated Reduction of Nitro and Azide Groups in the Presence of HCl in Aqueous Media
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Indium mediated reduction of azide and nitro groups in the presence of HCl (1.5 equiv based on indium) at room temperature in aqueous THF successfully provided the corresponding amine in high to quantitative yields. Under the some reaction conditions, selective reduction of azide and nitro group in the presence of vinyl group could be accomplished.
- Lee, Jung Gyu,Choi, Kyung Il,Koh, Hun Yeong,Kim, Youseung,Kang, Yonghan,Cho, Yong Seo
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- Palladium catalyzed cross-coupling reaction of Grignard reagents with halobenzoic acids, halophenols and haloanilines
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Convenient syntheses of substituted benzoic acids, phenols and anilines have been achieved by using palladium catalyzed cross-coupling reactions between Grignard reagents and aryl halides containing carboxy, hydroxy and amino groups without a protection-deprotection sequence.
- Bumagin, Nikolai A.,Luzikova, Elena V.
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p. 271 - 273
(2007/10/03)
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- Mechanistic studies of pyrene-sensitized decomposition of p-butylphenyl azide: generation of nitrene radical anion through a sensitizer-mediated electron transfer from amines to the azide
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Pyrene-sensitized photolysis of p-butylphenyl azide (1) in acetonitrile containing diethylamine (DEA) gave a mixture of the 3H-azepine (2) and p-butylaniline (3).In order to reveal the mechanism of the formation of these photoproducts, the effects of the DEA or sensitizer concentration, solvents and various additives on the product distribution have been examined.Thus, it is proposed that the azepine 2 mainly originates from the singlet nitrene formed through the energy transfer from the excited pyrene to the azide 1, while the one-electron reduction of 1 with the pyrene radical anion produced through the electron transfer from DEA to singlet excited pyrene is involved in the formation of the aniline 3.
- Murata, Shigeru,Nakatsuji, Ryuichi,Tomioka, Hideo
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p. 793 - 800
(2007/10/02)
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- LIQUID CRYSTALLINE PROPERTIES OF 4-CHLOROBENZYLIDENE-4-AKYLANILINES
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A new group of Schiff bases containing a polar terminal group was synthesized: .The alkyl was changed from n=1 to n=12.Based on calorimetric (DSC) studies and on observations of textures the phase situation was characterized.
- Galewski, Zbigniew
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p. 233 - 242
(2007/10/02)
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- Use of Liquid Crystal Induced Circular Dichroism for Absolute Configurational Assignments of β-Amino Alcohols
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Dissolution of small quantities of chiral β-amino alcohols in liquid crystalline N-(p-methoxybenzylidene)-p-n-butylaniline (MBBA) results in induced rotations due to the formation of a cholesteric (chiral) liquid crystal phase.The induced rotations are several orders of magnitude larger than those observed for β-amino alcohols in isotropic solutions, and the signs of these rotations can be correlated with the absolute configurations of the chiral amino alcohols when standard conformational analysis arguments and the preference of elongated molecules to align with MBBA are considered.
- Rinaldi, Peter L.,Wilk, Melody
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p. 2141 - 2146
(2007/10/02)
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- Reaction of Azomethine Moiety Buried in Bilayer Membranes
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The reaction with water and amines of the azomethine moiety that is part of single-chain ammonium amphiphiles was examined.These amphiphiles form stable bilayer aggregates when they have the alkyl tail of C7 or C12.The reaction with water of the bilayer-forming amphiphiles ceases at the hydration stage and are 10-2000 times slower than those of the amphiphiles which do not form bilayers and undergo hydrolytic cleavage.The reactivity of the azomethine moiety in bilayers decreases with increasing distance from the membrane surface.The Arrhenius plots for the bilayer-forming amphiphiles show discontinuities at temperatures corresponding to phase transition of the respective bilayer (Tc).The apparent activation energy is larger at temperatures below Tc than at temperatures above Tc.This suggests that water penetration is facilitated in the fluid bilayer.The reaction with amines was affected by their solubility in the bilayer matrix, and poly(ethylenimine) gave a much reduced reaction rate when the azomethine moiety was buried deep in the bilayer matrix.
- Okahata, Yoshio,Ando, Reiko,Kunitake, Toyoki
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p. 802 - 808
(2007/10/02)
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